US20190190077A1

US20190190077A1 - Nonaqueous electrolyte secondary battery

Info

Publication number: US20190190077A1
Application number: US16/224,788
Authority: US
Inventors: Ichiro Arise; Toshihiko Ogata; Chikae Yoshimaru; Chikara Murakami
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2017-12-19
Filing date: 2018-12-18
Publication date: 2019-06-20
Also published as: CN109935767A; JP2019110070A; JP6507220B1; CN109935767B; KR20190074257A

Abstract

The present invention provides a nonaqueous electrolyte secondary battery in which a good high-rate discharge capacity after charge-discharge cycles is maintained. The nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention includes: (i) a combination of a positive electrode plate and a negative electrode plate in which the sum of interface barrier energies is not less than a predetermined value, (ii) a nonaqueous electrolyte secondary battery separator that includes a porous film whose temperature rise ending period with respect to a resin amount per unit area at irradiation with microwave falls within a predetermined range, and (iii) a porous layer that contains an α-form polyvinylidene fluoride-based resin of a polyvinylidene fluoride-based resin at a predetermined proportion. The porous layer is provided between the nonaqueous electrolyte secondary battery separator and at least one of the positive electrode plate and the negative electrode plate.

Description

This Nonprovisional application claims priority under 35 U.S.C. § 119 on Patent Application No. 2017-243290 filed in Japan on Dec. 19, 2017, the entire contents of which are hereby incorporated by reference.

TECHNICAL FIELD

The present invention relates to a nonaqueous electrolyte secondary battery.

BACKGROUND ART

Nonaqueous electrolyte secondary batteries, in particular, lithium secondary batteries have a high energy density, and are thus in wide use as batteries for a personal computer, a mobile telephone, a portable information terminal, and the like. Such nonaqueous electrolyte secondary batteries have recently been developed as on-vehicle batteries.
For example, Patent Literature 1 discloses a nonaqueous electrolyte secondary battery which includes a separator having a temperature rise ending period that falls within a specific range when the separator is irradiated with a microwave.

CITATION LIST

Patent Literature

Patent Literature 1: Japanese Patent No. 6012838 (Publication Date: Oct. 25, 2016)

SUMMARY OF INVENTION

Technical Problem

The above nonaqueous electrolyte secondary battery unfortunately has room for improvement in maintaining a high-rate discharge capacity after charge-discharge cycles.
An object to be attained by an aspect of the present invention is to provide a nonaqueous electrolyte secondary battery in which a good high-rate discharge capacity after charge-discharge cycles is maintained.

Solution to Problem

The present invention encompasses the following features.
<1> A nonaqueous electrolyte secondary battery including: a nonaqueous electrolyte secondary battery separator including a polyolefin porous film; a porous layer containing a polyvinylidene fluoride-based resin; a positive electrode plate; and a negative electrode plate,
in a case where the positive electrode plate and the negative electrode plate have each been processed into a disk having a diameter of 15.5 mm and immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, a sum of respective interface barrier energies measured of a positive electrode active material and a negative electrode active material being not less than 5000 J/mol,
the polyolefin porous film having a temperature rise ending period of 2.9 seconds·m²/g to 5.7 seconds·m²/g with respect to an amount of resin per unit area in a case where the polyolefin porous film has been impregnated with N-methylpyrrolidone containing 3% by weight of water and has then been irradiated with a microwave having a frequency of 2455 MHz and an output of 1800 W,
the porous layer being present between the nonaqueous electrolyte secondary battery separator and the positive electrode plate and/or between the nonaqueous electrolyte secondary battery separator and the negative electrode plate,
the polyvinylidene fluoride-based resin contained in the porous layer containing an α-form polyvinylidene fluoride-based resin in an amount of not less than 35.0 mol % with respect to 100 mol % of a combined amount of the α-form polyvinylidene fluoride-based resin and a β-form polyvinylidene fluoride-based resin contained in the polyvinylidene fluoride-based resin,
a content of the α-form polyvinylidene fluoride-based resin being calculated by (i) waveform separation of (α/2) observed at around −78 ppm in a ¹⁹F-NMR spectrum obtained from the porous layer and (ii) waveform separation of {(α/2)+β} observed at around −95 ppm in the ¹⁹F-NMR spectrum obtained from the porous layer.
<2> The nonaqueous electrolyte secondary battery which is described in <1> and in which the positive electrode plate contains a transition metal oxide.
<3> The nonaqueous electrolyte secondary battery which is described in <1> or <2> and in which the negative electrode plate contains graphite.
<4> The nonaqueous electrolyte secondary battery which is described in any one of <1> through <3> and in which the nonaqueous electrolyte secondary battery further includes another porous layer which is provided between (i) the nonaqueous electrolyte secondary battery separator and (ii) at least one of the positive electrode plate and the negative electrode plate.
<5> The nonaqueous electrolyte secondary battery which is described in <4> and in which the another porous layer contains at least one resin selected from the group consisting of a polyolefin, a (meth)acrylate-based resin, a fluorine-containing resin (excluding a polyvinylidene fluoride-based resin), a polyamide-based resin, a polyester-based resin, and a water-soluble polymer.
<6> The nonaqueous electrolyte secondary battery which is described in <5> and in which the polyamide-based resin is aramid resin.

Advantageous Effects of Invention

According to an aspect of the present invention, it is possible to provide a nonaqueous electrolyte secondary battery in which a good high-rate discharge capacity after charge-discharge cycles is maintained.

DESCRIPTION OF EMBODIMENTS

The following description will discuss an embodiment of the present invention. The present invention is, however, not limited to the embodiment below. The present invention is not limited to the arrangements described below, but may be altered in various ways by a skilled person within the scope of the claims. Any embodiment based on a proper combination of technical means disclosed in different embodiments is also encompassed in the technical scope of the present invention. Note that numerical expressions such as “A to B” herein mean “not less than A and not more than B” unless otherwise stated.
[1. Nonaqueous Electrolyte Secondary Battery in Accordance with an Aspect of the Present Invention]
A nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention includes (i) a separator for a nonaqueous electrolyte secondary battery (hereinafter referred to as a “nonaqueous electrolyte secondary battery separator” or referred to simply as “separator”) including a polyolefin porous film (hereinafter referred to also as “porous film”), (ii) a porous layer containing a polyvinylidene fluoride-based resin, (iii) a positive electrode plate, and (iv) a negative electrode plate,
in a case where the positive electrode plate and the negative electrode plate have each been processed into a disk having a diameter of 15.5 mm and immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, a sum of respective interface barrier energies measured of a positive electrode active material and a negative electrode active material (hereinafter referred to also as “sum of the interface barrier energies) being not less than 5000 J/mol,
the polyolefin porous film having a temperature rise ending period of 2.9 seconds·m²/g to 5.7 seconds·m²/g with respect to an amount of resin per unit area in a case where the polyolefin porous film has been impregnated with N-methylpyrrolidone containing 3% by weight of water and has then been irradiated with a microwave having a frequency of 2455 MHz and an output of 1800 W,
the porous layer being provided between the nonaqueous electrolyte secondary battery separator and at least one of the positive electrode plate and the negative electrode plate,
the polyvinylidene fluoride-based resin contained in the porous layer containing an α-form polyvinylidene fluoride-based resin in an amount of not less than 35.0 mol % with respect to 100 mol % of a combined amount of the α-form polyvinylidene fluoride-based resin and a β-form polyvinylidene fluoride-based resin contained in the polyvinylidene fluoride-based resin,
a content of the α-form polyvinylidene fluoride-based resin being calculated by (i) waveform separation of (α/2) observed at around −78 ppm in a ¹⁹F-NMR spectrum obtained from the porous layer and (ii) waveform separation of {(α/2)+β} observed at around −95 ppm in the ¹⁹F-NMR spectrum obtained from the porous layer.
With a combination of the positive electrode plate and the negative electrode plate in which the sum of the interface barrier energies falls within the aforementioned range, ions and electric charge in the respective active material surfaces of the positive electrode active material layer and the negative electrode active material layer move uniformly during charge-discharge cycles. This makes the reactivity of the entire active material moderate and uniform and thus prevents (i) the internal structure of the active material layer from changing easily and (ii) the active material itself from degrading easily.
In the porous film having the temperature rise ending period that falls within the above described range when being irradiated with a microwave, a structure (i.e., capillary force in pores and an area of a wall of the pores) of the pores existing in the porous film falls within a specific range. In addition, such a porous film has a sufficiently high capability to supply an electrolyte from the porous film to the electrodes. As a result, drying up of the electrolyte in the pores and blockage of the pores are prevented.
The porous layer in which a rate of content of an α-form polyvinylidene fluoride-based resin in the polyvinylidene fluoride-based resin falls within the above described range can inhibit plastic deformation of the polyvinylidene fluoride-based resin at a high temperature. As a result, structural deformation of the porous layer and blockage of voids in the porous layer are prevented.
By selecting the above constituent members, the nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention brings about a novel effect of maintaining a good high-rate discharge capacity after charge-discharge cycles. As a specific example, in the nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention, a good discharge capacity at 5 C after 100 charge-discharge cycles is maintained, as compared with a conventional nonaqueous electrolyte secondary battery.
According to the nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention, a discharge capacity at 5 C after 100 charge-discharge cycles is preferably not less than 120 mAh/g, more preferably not less than 125 mAh/g, and even more preferably not less than 130 mAh/g.
The discharge capacity at 5 C after 100 charge-discharge cycles can be calculated by the following procedures (1) through (3): Note that “1 C” hereinafter refers to a value of an electric current at which a battery rated capacity defined as a one-hour rate discharge capacity is discharged in one hour. The “CC-CV charge” refers to a charging method in which (i) a battery is charged at a constant electric current until a certain voltage is reached, and (ii) after that, the battery is charged while the electric current is being reduced so that the certain voltage is maintained. The “CC discharge” refers to a discharging method in which a battery is discharged at a constant electric current until a certain voltage is reached.
(1) A prepared nonaqueous electrolyte secondary battery is subjected to four cycles of initial charge and discharge at 25° C. Each of the four cycles of initial charge and discharge is carried out as follows. Specifically, each of the four cycles of initial charge and discharge is carried out at a voltage ranging from 2.7 V to 4.1 V, with (i) CC-CV charge at a charge current value of 0.2 C (terminal current condition: 0.02 C) and then with (ii) CC discharge at a discharge current value of 0.2 C.
(2) The nonaqueous electrolyte secondary battery having been subjected to the initial charge and discharge is subjected to 100 cycles of cycle test at 55° C. Each of the 100 cycles of cycle test is carried out as follows. Specifically, each of the 100 cycles of cycle test is carried out at a voltage ranging from 2.7 V to 4.2 V, with (i) CC-CV charge at a charge current value of 1 C (terminal current condition: 0.02 C) and then with (ii) CC discharge at a discharge current value of 10 C.
(3) Measurement of a discharge capacity at 5 C after cycles is made on the nonaqueous electrolyte secondary battery having been subjected to the cycle test.
Specifically, charge and discharge are carried out at a voltage ranging from 2.7 V to 4.2 V, with (i) CC-CV charge at a charge current value of 1 C (terminal current condition: 0.02 C) and then with (ii) CC discharge at discharge current values of 0.2 C, 1 C, and 5 C in this order. Three cycles of charge and discharge are carried out for each rate. A discharge capacity at a discharge current value of 5 C is used as the “discharge capacity at 5 C after 100 charge-discharge cycles”.
[2. Positive Electrode Plate and Negative Electrode Plate]
(Positive Electrode Plate)
The positive electrode plate included in a nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is not limited to any particular one as long as the following requirement is met: In a case where the positive electrode plate and the negative electrode plate (described later) have each been processed into a disk having a diameter of 15.5 mm and immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, the sum of the respective interface barrier energies measured of the positive electrode plate and the negative electrode plate is not less than 5000 J/mol. For example, the positive electrode plate is a sheet-shaped positive electrode plate including, (i) as a positive electrode active material layer, a positive electrode mix containing a positive electrode active material, an electrically conductive agent, and a binding agent and (ii) a positive electrode current collector supporting the positive electrode mix thereon. Note that the positive electrode plate may be configured such that the positive electrode current collector supports the positive electrode mix on both surfaces thereof or on one of the surfaces thereof.
The positive electrode active material is, for example, a material capable of being doped with and dedoped of lithium ions. Such a material is preferably transition metal oxide. Examples of the transition metal oxide encompass lithium complex oxides containing at least one transition metal including, for example, V, Mn, Fe, Co, and Ni. Among such lithium complex oxides, (i) a lithium complex oxide having an α-NaFeO₂structure such as lithium nickelate and lithium cobaltate and (ii) a lithium complex oxide having a spinel structure such as lithium manganese spinel are preferable because such lithium complex oxides have a high average discharge potential. The lithium complex oxide may further contain any of various metallic elements, and is further preferably complex lithium nickelate.
Further, the complex lithium nickelate furthermore preferably contains at least one metallic element selected from the group consisting of Ti, Zr, Ce, Y, V, Cr, Mn, Fe, Co, Cu, Ag, Mg, Al, Ga, In, and Sn at a proportion of 0.1 mol % to 20 mol % with respect to the sum of the number of moles of the at least one metallic element and the number of moles of Ni in the lithium nickelate. This is because such a complex lithium nickelate allows an excellent cycle characteristic for use in a high-capacity battery. Among others, an active material that contains Al or Mn and that contains Ni at a proportion of not less than 85%, further preferably not less than 90%, is particularly preferable because a nonaqueous electrolyte secondary battery including a positive electrode plate containing the above active material has an excellent cycle characteristic for use as a high-capacity battery.
Examples of the electrically conductive agent include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fiber, and a fired product of an organic polymer compound. The present embodiment may use (i) only one kind of the above electrically conductive agents or (ii) two or more kinds of the above electrically conductive agents in combination, for example a mixture of artificial graphite and carbon black.
Examples of the binding agent include thermoplastic resins such as polyvinylidene fluoride, a copolymer of vinylidene fluoride, polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, a thermoplastic polyimide, polyethylene, and polypropylene; an acrylic resin; and styrene-butadiene rubber. The binding agent functions also as a thickening agent.
The positive electrode mix may be prepared by, for example, a method of applying pressure to the positive electrode active material, the electrically conductive agent, and the binding agent on the positive electrode current collector or a method of using an appropriate organic solvent so that the positive electrode active material, the electrically conductive agent, and the binding agent are in a paste form.
Examples of the positive electrode current collector include electric conductors such as Al, Ni, and stainless steel. Among these, Al is preferable as it is easy to process into a thin film and less expensive.
The sheet-shaped positive electrode plate may be produced, that is, the positive electrode mix may be supported by the positive electrode current collector, through, for example, a method of applying pressure to the positive electrode active material, the electrically conductive agent, and the binding agent on the positive electrode current collector to form a positive electrode mix on the positive electrode current collector or a method of (i) using an appropriate organic solvent so that the positive electrode active material, the electrically conductive agent, and the binding agent are in a paste form to provide a positive electrode mix, (ii) applying the positive electrode mix to the positive electrode current collector, (iii) drying the applied positive electrode mix to prepare a sheet-shaped positive electrode mix, and (iv) applying pressure to the sheet-shaped positive electrode mix so that the sheet-shaped positive electrode mix is firmly fixed to the positive electrode current collector.
The particle diameter of the positive electrode active material is expressed as, for example, an average particle diameter (D50) per volume. The positive electrode active material normally has an average particle diameter per volume of approximately 0.1 μm to 30 μm. The average particle diameter (D50) per volume of the positive electrode active material can be measured with use of a laser diffraction particle size analyzer (product name: SALD2200, available from Shimadzu Corporation).
The positive electrode active material normally has an aspect ratio (that is, the long-axis diameter/the short-axis diameter) of approximately 1 to 100. The aspect ratio of the positive electrode active material can be determined by the following method: In an SEM image formed by observing the positive electrode active material on a flat surface from above in a direction perpendicular to the surface, the average is calculated (as the aspect ratio) of the ratios of the respective long-axis dimensions (long-axis diameters) and short-axis dimensions (short-axis diameters) of 100 particles of the positive electrode active material which 100 particles do not coincide with one another in the thickness direction of the positive electrode active material.
The positive electrode active material layer normally has a porosity of approximately 10% to 80%. The porosity (c) of the positive electrode active material layer can be calculated, by the formula below, from a density p (g/m³) of the positive electrode active material layer, respective mass compositions (weight %) b′, b², . . . bⁿof materials that constitute the positive electrode active material layer (e.g., a positive electrode active material, an electrically conductive agent, a binding agent, and others), and respective real densities (g/m³) c¹, c², . . . cⁿof these materials. Note here that the real densities of the materials may be literature data or may be measured values obtained by a pycnometer method.
ε=1−{ρ×(b ¹/100)/c ¹+ρ×(b ²/100)/c ²+ . . . ρ×(b ⁿ/100)/c ⁿ}×100
The positive electrode active material layer normally contains a positive electrode active material at a proportion of not less than 70% by weight.
The coating line speed (that is, a speed at which a positive electrode mix containing a positive electrode active material is applied to a current collector; hereinafter referred to also as “coating speed”) is within a range of 10 m/min to 200 m/min. The coating line speed during the coating operation can be adjusted by appropriately setting the device for applying a positive electrode active material.
(Negative Electrode Plate)
The negative electrode plate included in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is not limited to any particular one as long as the following requirement is met: In a case where the positive electrode plate and the negative electrode plate have each been processed into a disk having a diameter of 15.5 mm and immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, the sum of the respective interface barrier energies measured of the positive electrode plate and the negative electrode plate is not less than 5000 J/mol. For example, the negative electrode plate is a sheet-shaped negative electrode plate including, (i) as a negative electrode active material layer, a negative electrode mix containing a negative electrode active material and (ii) a negative electrode current collector supporting the negative electrode mix thereon. Note that the negative electrode plate may be configured such that the negative electrode current collector supports the negative electrode mix on both surfaces thereof or on one of the surfaces thereof.
The sheet-shaped negative electrode plate preferably contains the above electrically conductive agent and binding agent.
Examples of the negative electrode active material include (i) a material capable of being doped with and dedoped of lithium ions, (ii) lithium metal, and (iii) lithium alloy. Specific examples of the material include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fiber, and a fired product of an organic polymer compound; chalcogen compounds such as an oxide and a sulfide that are doped and dedoped with lithium ions at an electric potential lower than that for the positive electrode plate; metals such as Al, Pb, Sn, Bi, or Si, each of which is alloyed with alkali metal; an intermetallic compound (AlSb, Mg₂Si, NiSi₂) of a cubic system in which intermetallic compound alkali metal can be inserted in voids in a lattice; and a lithium nitrogen compound (Li_3-xM_xN (where M represents a transition metal)). Of the above negative electrode active materials, a negative electrode active material containing graphite is preferable, and a carbonaceous material that contains, as a main component, a graphite material such as natural graphite or artificial graphite is more preferable. This is because such graphite and a carbonaceous material are high in potential evenness, and a great energy density can be obtained in a case where the graphite or carbonaceous material, which is low in average discharge potential, is combined with the positive electrode plate. The negative electrode active material may alternatively be a mixture of graphite and silicon, preferably containing Si at a proportion of not less than 5%, more preferably not less than 10%, with respect to C in the graphite.
The negative electrode mix may be prepared by, for example, a method of applying pressure to the negative electrode active material on the negative electrode current collector or a method of using an appropriate organic solvent so that the negative electrode active material is in a paste form.
Examples of the negative electrode current collector encompass Cu, Ni, and stainless steel. Among these, Cu is preferable as it is not easily alloyed with lithium particularly in a lithium-ion secondary battery and is easily processed into a thin film.
The sheet-shaped negative electrode plate may be produced, that is, the negative electrode mix may be supported by the negative electrode current collector, through, for example, a method of applying pressure to the negative electrode active material on the negative electrode current collector to form a negative electrode mix thereon or a method of (i) using an appropriate organic solvent so that the negative electrode active material is in a paste form to provide a negative electrode mix, (ii) applying the negative electrode mix to the negative electrode current collector, (iii) drying the applied negative electrode mix to prepare a sheet-shaped negative electrode mix, and (iv) applying pressure to the sheet-shaped negative electrode mix so that the sheet-shaped negative electrode mix is firmly fixed to the negative electrode current collector. The above paste preferably includes the above electrically conductive agent and binding agent.
The negative electrode active material normally has an average particle diameter (D50) per volume of approximately 0.1 μm to 30 μm.
The negative electrode active material normally has an aspect ratio (that is, the long-axis diameter/the short-axis diameter) of approximately 1 to 10.
The negative electrode active material layer normally has a porosity of approximately 10% to 60%.
The negative electrode active material layer normally contains a negative electrode active material at a proportion of not less than 70% by weight, preferably not less than 80% by weight, more preferably not less than 90% by weight.
The coating line speed (that is, a speed at which a negative electrode mix containing a negative electrode active material is applied to a current collector; hereinafter referred to also as “coating speed”) is within a range of 10 m/min to 200 m/min. The coating line speed during the coating operation can be adjusted by appropriately setting the device for applying a negative electrode active material.
The methods described under “(Positive electrode plate)” can be used to determine the particle diameter, aspect ratio, and porosity of the negative electrode active material, the proportion of the negative electrode active material in the negative electrode active material layer, and the coating speed.
(Sum of Interface Barrier Energies)
In a case where the positive electrode plate and the negative electrode plate in accordance with an embodiment of the present invention have each been (i) processed into a disk having a diameter of 15.5 mm and (ii) immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, the sum of the respective interface barrier energies measured of the positive electrode plate and the negative electrode plate is not less than 5000 J/mol. The sum of the interface barrier energies is preferably not less than 5100 J/mol, more preferably not less than 5200 J/mol.
In a case where the sum of the interface barrier energies is not less than 5000 J/mol, the active material surface in the active material layer allows ions and electric charge to move uniformly, and the reactivity of the entire active material layer is moderate and uniform as a result. This should prevent (i) the internal structure of the active material layer from changing easily and (ii) the active material itself from degrading easily.
If the sum of the interface barrier energies is less than 5000 J/mol, the reactivity of the active material layer will be non-uniform, whereby the internal structure of the active material layer will be changed locally, and the active material will be degraded partially (for example, generation of gas).
For the above reason, the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention, in which the sum of the respective interface barrier energies of the positive electrode plate and the negative electrode plate is not less than 5000 J/mol, advantageously maintains a good high-rate discharge capacity after charge-discharge cycles.
The sum of the interface barrier energies has no particular upper limit. If the sum of the interface barrier energies is excessively high, however, that will undesirably prevent ions and electric charge from moving at the active material surface and thereby prevent the active material from being easily subjected to oxidation-reduction reaction resulting from charge and discharge. The sum of the interface barrier energies has an upper limit of, for example, approximately 15,000 J/mol.
The above-described sum of the interface barrier energies is determined by measuring the respective interface barrier energies of the positive electrode active material and the negative electrode active material and calculating the sum of the interface barrier energies through the procedure below.
(1) The positive electrode plate and the negative electrode plate are each cut into a disk having a diameter of 15 mm. The polyolefin porous film is also cut into a disk having a diameter of 17 mm for use as a separator.
(2) A mixed solvent is prepared that contains ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) at a volume ratio of 3:5:2. LiPF₆is dissolved in the mixed solvent at 1 mol/L for preparation of electrolyte.
(3) In a CR2032-type electrolytic bath, the negative electrode plate, the separator, the positive electrode plate, a stainless-steel plate (with a diameter of 15.5 mm and a thickness of 0.5 mm), and a waved washer are disposed on top of each other in this order from the bottom of the electrolytic bath. Then, the electrolyte is injected into the electrolytic bath, and the electrolytic bath is lidded, with the result of a coin cell being prepared.
(4) The coin cell prepared is placed in a thermostat bath. An alternating current impedance apparatus (FRA 1255B, available from Solartron) and CellTest System (1470E) are used at a frequency of 1 MHz to 0.1 Hz and a voltage amplitude of 10 mV to draw a Nyquist plot. The thermostat bath has a temperature of 50° C., 25° C., 5° C., or −10° C.
(5) The diameter of a half arc (or an arc of a flat circle) of the Nyquist plot drawn is used to determine the resistance r₁+r₂of the positive electrode plate and the negative electrode plate at the electrode active material interface for different temperatures. The resistance r₁+r₂is the sum of the resistance of the positive electrode and the negative electrode to ion movement and the resistance of the positive electrode and the negative electrode to electric charge movement. The half arc may be two completely separate arcs or a flat circle made of two overlapping circles. The sum of the interface barrier energies is calculated in accordance with Expressions (1) and (2) below.
k=1/(r ₁ +r ₂)=A exp(−Ea/RT) Expression (1)
ln(k)=ln{1/(r ₁ +r ₂)}=ln(A)−Ea/RT Expression (2)
Ea: Sum of interface barrier energies (J/mol)
k: Transfer constant
r₁+r₂: Resistance (Ω)
A: Frequency factor
R: Gas constant=8.314 J/mol/K
T: Temperature of the thermostat bath (K)
Expression (2) is an expression in which natural logarithms of both sides of Expression (1) are taken. In Expression (2), ln{1/(r₁+r₂)} is a linear function of 1/T. Thus, Ea/R is determined from the inclination of an approximate line obtained by plotting the results of substituting the resistance value at each temperature into Expression (2). Substituting the gas constant R into Ea/R allows the sum Ea of the respective interface barrier energies to be calculated.
The frequency factor A is a unique value that does not vary according to temperature changes. This value is determined depending on, for example, the molar concentration of lithium ions in the electrolyte bulk. According to Expression (2), the frequency factor A is the value of ln(1/r₀) for a case where (1/T)=0, and can be calculated on the basis of the above approximate line.
The sum of the interface barrier energies can be controlled on the basis of, for example, the ratio of the respective particle diameters of the positive electrode active material and the negative electrode active material. The ratio of the respective particle diameters of the positive electrode active material and the negative electrode active material, that is, (the particle diameter of the negative electrode active material/the particle diameter of the positive electrode active material), is preferably not more than 6.0. If (the particle diameter of the negative electrode active material/the particle diameter of the positive electrode active material) gives an excessively large value, the sum of the interface barrier energies tends to be excessively small.
[3. Nonaqueous Electrolyte Secondary Battery Separator]
The nonaqueous electrolyte secondary battery separator in accordance with an embodiment of the present invention includes a polyolefin porous film.
The porous film may by itself serve as a nonaqueous electrolyte secondary battery separator. The porous film itself can also be a base material of a nonaqueous electrolyte secondary battery laminated separator in which a porous layer (described later) is disposed on the porous film. The porous film contains polyolefin as a main component and has a large number of pores connected to one another, and allows a gas or a liquid to pass therethrough from one surface to the other.
The nonaqueous electrolyte secondary battery separator in accordance with an embodiment of the present invention may be provided with a porous layer (described later) that contains a polyvinylidene fluoride-based resin and is disposed on at least one surface of the nonaqueous electrolyte secondary battery separator. This laminated body, in which the porous layer is disposed on at least one surface of the nonaqueous electrolyte secondary battery separator, is referred to in the present specification as a “nonaqueous electrolyte secondary battery laminated separator” or a “laminated separator”. Further, the nonaqueous electrolyte secondary battery separator in accordance with an embodiment of the present invention may include, in addition to a polyolefin porous film, another layer(s) such as an adhesive layer, a heat-resistant layer, and/or a protective layer.
The porous film contains a polyolefin at a proportion of not less than 50% by volume, preferably not less than 90% by volume, more preferably not less than 95% by volume, relative to the entire porous film. The polyolefin preferably contains a high molecular weight component having a weight-average molecular weight within a range of 5×10⁵to 15×10⁶. In particular, the polyolefin more preferably contains a high molecular weight component having a weight-average molecular weight of not less than 1,000,000 because such a polyolefin allows the nonaqueous electrolyte secondary battery separator to have a higher strength.
Specific examples of the polyolefin (thermoplastic resin) include a homopolymer or a copolymer each produced by (co)polymerizing a monomer such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, or 1-hexene. Examples of the homopolymer include polyethylene, polypropylene, and polybutene. Examples of the copolymer include an ethylene-propylene copolymer.
Among the above examples, polyethylene is preferable as it is capable of preventing (shutting down) a flow of an excessively large electric current at a lower temperature. Examples of the polyethylene include low-density polyethylene, high-density polyethylene, linear polyethylene (ethylene-α-olefin copolymer), and ultra-high molecular weight polyethylene having a weight-average molecular weight of not less than 1,000,000. Among these examples, ultra-high molecular weight polyethylene having a weight-average molecular weight of not less than 1,000,000 is further preferable.
The porous film has a film thickness of preferably 4 μm to 40 μm, more preferably 5 μm to 30 μm, still more preferably 6 μm to 15 μm.
The porous film only needs to have a weight per unit area which weight is determined as appropriate in view of the strength, film thickness, weight, and handleability of the separator. Note, however, that the porous film has a weight per unit area of preferably 4 g/m²to 20 g/m², more preferably 4 g/m²to 12 g/m², still more preferably 5 g/m²to 12 g/m², so as to allow a nonaqueous electrolyte secondary battery that includes a nonaqueous electrolyte secondary battery separator including the porous film to have a higher weight energy density and a higher volume energy density.
The porous film has an air permeability of preferably 30 sec/100 mL to 500 sec/100 mL, more preferably 50 sec/100 mL to 300 sec/100 mL, in terms of Gurley values. A porous film having an air permeability within the above range can have sufficient ion permeability.
The porous film has a porosity of preferably 20% by volume to 80% by volume, more preferably 30% by volume to 75% by volume, so as to (i) retain a larger amount of electrolyte and (ii) obtain the function of reliably preventing (shutting down) a flow of an excessively large electric current at a lower temperature. Further, in order to obtain sufficient ion permeability and prevent particles from entering the positive electrode and/or the negative electrode, the porous film has pores each having a diameter of preferably not larger than 0.3 μm, more preferably not larger than 0.14 μm.
(Temperature Rise Ending Period of Porous Film)
Irradiating a porous film containing N-methylpyrrolidone containing water with a microwave causes the porous film to generate heat due to vibrational energy of the water. The heat generated is transferred to the resin contained in the porous film which resin is in contact with the N-methylpyrrolidone containing water. The temperature rise ends when equilibrium is reached between (i) the rate of heat generation and (ii) the rate of cooling due to transfer of heat to the resin. This indicates that the temperature rise ending period is related to the degree of contact between (i) the liquid contained in the porous film (in this example, N-methylpyrrolidone containing water) and (ii) the resin contained in the porous film. The degree of contact between the liquid contained in the porous film and the resin contained in the porous film is closely related to the capillary force in the pores of the porous film and the area of the wall of the pores. Thus, the temperature rise ending period can be used for evaluation of the structure of pores of a porous film. Specifically, a shorter temperature rise ending period indicates that the capillary force in the pores is larger and that the area of the wall of the pores is larger.
The degree of contact between the liquid contained in the porous film and the resin contained in the porous film is presumably larger in a case where the liquid moves more easily through the pores of the porous film. This makes it possible to use the temperature rise ending period for evaluation of the capability to supply an electrolyte from the porous film to the electrodes. Specifically, a shorter temperature rise ending period indicates a higher capability to supply an electrolyte from the porous film to the electrodes.
A porous film in accordance with an aspect of the present invention has a temperature rise ending period of 2.9 seconds·m²/g to 5.7 seconds·m²/g, preferably 2.9 seconds·m²/g to 5.3 seconds·m²/g, with respect to the amount of resin per unit area (weight per unit area). Note that a temperature of the porous film that has been impregnated with N-methylpyrrolidone containing 3% by weight of water falls within a range of 29° C.±1° C. when irradiation with a microwave is initiated. The temperature rise ending period is measured under atmospheric air while an inside temperature of the device is a normal temperature (e.g., 30° C.±3° C.).
If the temperature rise ending period with respect to the amount of resin per unit area is less than 2.9 seconds·m²/g, both the capillary force in the pores of the porous film and the area of the wall of the pores may become excessively large. This may lead to an increase in the stress caused on the wall of the pores when the electrolyte moves through the pores during a charge-discharge cycle and/or during use of the battery with a large electric current. This may in turn block the pores, with the result of degradation in the discharge capacity after the charge-discharge cycle.
If the temperature rise ending period with respect to the amount of resin per unit area is more than 5.7 seconds·m²/g, liquid will move less easily through the pores of the porous film, and in a case where the porous film is used as a separator for a nonaqueous electrolyte secondary battery, the electrolytic solution will move more slowly near the interface between the porous film and an electrode, with the result of a decrease in the rate characteristic of the battery. In addition, when the battery has been charged and discharged repeatedly, the electrolyte will be more likely dried up locally at the interface between the separator and an electrode or inside the porous film. This may in turn lead to an increase in the internal resistance of the battery, and further cause degradation in the discharge capacity after the charge-discharge cycle.
In a case where the porous film having the temperature rise ending period of 2.9 seconds·m²/g to 5.7 seconds·m²/g with respect to the amount of resin per unit area is employed as a constituent member, the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention brings about the effect of maintaining a good high-rate discharge capacity after charge-discharge cycles.
Note that in a case where a porous film is provided with a porous layer or another layer each disposed on the porous film, the physical property values of the porous film, which is included in a laminated body including the porous film and a porous layer or another layer, can be measured after the porous layer or other layer is removed from the laminated body. The porous layer or other layer can be removed from the laminated body by, for example, a method of dissolving the resin of the porous layer or other layer with use of a solvent such as N-methylpyrrolidone or acetone for removal.
The porous film in accordance with an embodiment of the present invention can be produced by, for example, a method as follows:
In a case where a porous film is provided with a porous layer disposed on the porous film, the physical property values of the porous film, which is included in a laminated separator including the porous film and a porous layer, can be measured after the porous layer is removed from the laminated separator. The porous layer can be removed from the laminated separator by, for example, a method of dissolving the resin of the porous layer with use of a solvent such as N-methylpyrrolidone or acetone for removal.
The following description discusses a method for producing the porous film. The porous film which contains a polyolefin-based resin as a main component, e.g., the porous film which is made of polyolefin resin containing (i) ultra-high molecular weight polyethylene and (ii) low molecular weight polyolefin having a weight-average molecular weight of not more than 10,000 is preferably produced by such a method as described below.
Specifically, the porous film can be obtained by a method including the steps of (1) obtaining a polyolefin resin composition by kneading (i) ultra-high molecular weight polyethylene, (ii) a low molecular weight polyolefin having a weight-average molecular weight of not more than 10,000, and (iii) a pore forming agent such as calcium carbonate or a plasticizing agent, (2) forming (rolling) a sheet with use of reduction rollers to roll the polyolefin resin composition obtained in the step (1), (3) removing the pore forming agent from the sheet obtained in the step (2), and (4) obtaining a porous film by stretching the sheet obtained in the step (3).
The structure of pores of the porous film is influenced by the following two factors. That is, the first factor is the straining rate during the stretching in the step (4). The second factor is a heat-fixation temperature per unit thickness of the stretched film during a heat-fixation treatment (annealing treatment) after the stretching. Examples of the structure of the pores of the porous film influenced by those factors include the capillary force of the pores, the area of the wall of the pores, and stress remaining in the porous film.
Thus, in a case where the straining rate and the heat-fixation temperature per unit thickness of the stretched film have been adjusted, controlling the structure of the pores of the porous film makes it possible to control the temperature rise ending period with respect to the amount of resin per unit area.
Specifically, a porous film included in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention tends to be produced in a case where the straining rate and the heat-fixation temperature per unit thickness of the stretched film have been so adjusted as to fall, on a graph having an X axis indicative of the straining rate and a Y axis indicative of the heat-fixation temperature per unit thickness of the stretched film, within a triangular area having three vertices at (i) 500% per minute and 1.5° C./μm, (ii) 900% per minute and 14.0° C./μm, and (iii) 2500% per minute and 11.0° C./μm. The straining rate and the heat-fixation temperature per unit thickness of the stretched film are preferably so adjusted as to fall within a triangular area having three vertices at (i) 600% per minute and 5.0° C./μm, (ii) 900% per minute and 12.5° C./μm, and (iii) 2500% per minute and 11.0° C./μm.
[4. Porous Layer]
For an embodiment of the present invention, the porous layer is disposed, as a member of a nonaqueous electrolyte secondary battery, between (i) the nonaqueous electrolyte secondary battery separator and (ii) at least one of the positive electrode plate and the negative electrode plate. The porous layer may be present on one surface or both surfaces of the nonaqueous electrolyte secondary battery separator. The porous layer may alternatively be disposed on an active material layer of at least one of the positive electrode plate and the negative electrode plate. The porous layer may alternatively be provided between the nonaqueous electrolyte secondary battery separator and at least one of the positive electrode plate and the negative electrode plate in such a manner as to be in contact with the nonaqueous electrolyte secondary battery separator and the at least one of the positive electrode plate and the negative electrode plate. There may be a single porous layer or two or more porous layers between the nonaqueous electrolyte secondary battery separator and at least one of the positive electrode plate and the negative electrode plate.
The porous layer is preferably an insulating porous layer.
It is preferable that a resin that may be contained in the porous layer be insoluble in the electrolyte of the battery and be electrochemically stable when the battery is in normal use. In a case where the porous layer is disposed on one surface of the porous film, the porous layer is preferably disposed on that surface of the porous film which surface faces the positive electrode plate of the nonaqueous electrolyte secondary battery, more preferably on that surface of the porous film which surface comes into contact with the positive electrode plate.
The porous layer in an embodiment of the present invention contains a polyvinylidene fluoride-based resin (PVDF-based resin), the PVDF-based resin containing a PVDF-based resin having crystal form α (hereinafter referred to as an α-form PVDF-based resin) in an amount of not less than 35.0 mol % relative to 100 mol % of the combined amount of the α-form PVDF-based resin and a PVDF-based resin having crystal form β (hereinafter, referred to as a β-form PVDF-based resin) contained in the PVDF-based resin.
Note here that the content of the α-form PVDF-based resin is calculated by (i) waveform separation of (α/2) observed at around −78 ppm in a ¹⁹F-NMR spectrum obtained from the porous layer and (ii) waveform separation of {(α/2)+β} observed at around −95 ppm in the ¹⁹F-NMR spectrum obtained from the porous layer.
The porous layer contains a large number of pores connected to one another, and thus allows a gas or a liquid to pass therethrough from one surface to the other. Further, in a case where the porous layer in accordance with an embodiment of the present invention is used as a constituent member of a nonaqueous electrolyte secondary battery laminated separator, the porous layer can be a layer capable of adhering to an electrode as the outermost layer of the separator.
Examples of the PVDF-based resin include homopolymers of vinylidene fluoride, copolymers of vinylidene fluoride and other monomer(s) copolymerizable with vinylidene fluoride, and mixtures of the above polymers. Examples of the monomer copolymerizable with vinylidene fluoride include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, trichloroethylene, and vinyl fluoride. The present invention can use (i) one kind of monomer or (ii) two or more kinds of monomers selected from above. The PVDF-based resin can be synthesized through emulsion polymerization or suspension polymerization.
The PVDF-based resin contains vinylidene fluoride at a proportion of normally not less than 85 mol %, preferably not less than 90 mol %, more preferably not less than 95 mol %, further preferably not less than 98 mol %. A PVDF-based resin containing vinylidene fluoride at a proportion of not less than 85 mol % is more likely to allow a porous layer to have a mechanical strength against pressure and a heat resistance against heat during battery production.
The porous layer can also preferably contain two kinds of PVDF-based resins that differ from each other in terms of, for example, the hexafluoropropylene content. Examples of such a porous layer includes a porous layer containing two kinds of PVDF-based resins (i.e., a first resin and a second resin) below.
The first resin is (i) a vinylidene fluoride-hexafluoropropylene copolymer containing hexafluoropropylene at a proportion of more than 0 mol % and not more than 1.5 mol % or (ii) a vinylidene fluoride homopolymer.
The second resin is a vinylidene fluoride-hexafluoropropylene copolymer containing hexafluoropropylene at a proportion of more than 1.5 mol %.
A porous layer containing the two kinds of PVDF-based resins adheres better to an electrode than a porous layer not containing one of the two kinds of PVDF-based resins. Further, a porous layer containing the two kinds of PVDF-based resins adheres better to another layer (for example, the porous film layer) included in a nonaqueous electrolyte secondary battery separator than a porous layer not containing one of the two kinds of PVDF-based resins, with the result of a higher peel strength between the two layers. The first resin and the second resin preferably have a mass ratio of 15:85 to 85:15.
The PVDF-based resin has a weight-average molecular weight of preferably 200,000 to 3,000,000, more preferably 200,000 to 2,000,000, even more preferably 500,000 to 1,500,000. A PVDF-based resin having a weight-average molecular weight of not less than 200,000 tends to allow a porous layer and an electrode to adhere to each other sufficiently. A PVDF-based resin having a weight-average molecular weight of not more than 3,000,000 tends to allow for excellent shaping easiness.
The porous layer in accordance with an embodiment of the present invention may contain a resin other than the PVDF-based resin. Examples of the other resin include: a styrene-butadiene copolymer; homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile; and polyethers such as polyethylene oxide and polypropylene oxide.
The porous layer in accordance with an embodiment of the present invention may contain a filler. The filler may be a filler such as an inorganic filler (for example, fine metal oxide particles) or an organic filler. The filler is contained at a proportion of preferably not less than 1% by mass and not more than 99% by mass, more preferably not less than 10% by mass and not more than 98% by mass, relative to the combined amount of the PVDF-based resin and the filler. The proportion of the filler may have a lower limit of not less than 50% by mass, not less than 70% by mass, or not less than 90% by mass. The filler such as the organic or inorganic filler may be a conventionally publicly known filler.
The porous layer in accordance with an embodiment of the present invention has an average thickness of preferably 0.5 μm to 10 μm, more preferably 1 μm to 5 μm, per layer in order to ensure adhesion to an electrode and a high energy density.
A porous layer having a film thickness of less than 0.5 μm per layer is preferable because such a porous layer can (i) reduce the possibility of internal short circuiting resulting from, for example, a breakage of the nonaqueous electrolyte secondary battery and (ii) retain a sufficient amount of electrolyte.
If the porous layer has a thickness of more than 10 μm per layer, the nonaqueous electrolyte secondary battery will have an increased resistance to permeation of lithium ions. Thus, repeating charge-and-discharge cycles will degrade the positive electrode of the nonaqueous electrolyte secondary battery, with the result of a degraded rate characteristic and a degraded cycle characteristic. Further, such a porous layer will increase the distance between the positive electrode and the negative electrode, with the result of a decrease in the internal capacity efficiency of the nonaqueous electrolyte secondary battery.
The porous layer in accordance with the present embodiment is preferably disposed between the nonaqueous electrolyte secondary battery separator and the positive electrode active material layer of the positive electrode plate. The descriptions below of the physical properties of the porous layer are at least descriptions of the physical properties of a porous layer disposed between the nonaqueous electrolyte secondary battery separator and the positive electrode active material layer of the positive electrode plate in a nonaqueous electrolyte secondary battery.
The porous layer only needs to have a weight per unit area (per layer) which weight is appropriately determined in view of the strength, film thickness, weight, and handleability of the nonaqueous electrolyte secondary battery laminated separator. The material(s) of the porous layer is applied in an amount (weight per unit area) of preferably 0.5 g/m²to 20 g/m², more preferably 0.5 g/m²to 10 g/m², per layer.
A porous layer having a weight per unit area which weight falls within the above numerical range allows a nonaqueous electrolyte secondary battery including the porous layer to have a higher weight energy density and a higher volume energy density. If the weight per unit area of the porous layer is beyond the above range, the nonaqueous electrolyte secondary battery will be heavy.
The porous layer has a porosity of preferably 20% by volume to 90% by volume, more preferably 30% by volume to 80% by volume, in order to achieve sufficient ion permeability. The pore diameter of the pores in the porous layer is preferably not more than 1.0 μm, more preferably not more than 0.5 μm. In a case where the pores each have such a pore diameter, a nonaqueous electrolyte secondary battery that includes the porous layer can achieve sufficient ion permeability.
The nonaqueous electrolyte secondary battery laminated separator has an air permeability of preferably 30 sec/100 mL to 1000 sec/100 mL, more preferably 50 sec/100 mL to 800 sec/100 mL, in terms of Gurley values. The nonaqueous electrolyte secondary battery laminated separator, which has the above air permeability, allows the nonaqueous electrolyte secondary battery to have sufficient ion permeability.
An air permeability smaller than the above range means that the nonaqueous electrolyte secondary battery laminated separator has a high porosity and thus has a coarse laminated structure. This may result in a nonaqueous electrolyte secondary battery laminated separator having a lower strength and thus having an insufficient shape stability at high temperatures in particular. An air permeability larger than the above range may, on the other hand, prevent the nonaqueous electrolyte secondary battery laminated separator from having sufficient ion permeability and thus degrade the battery characteristics of the nonaqueous electrolyte secondary battery.
(Crystal Forms of PVDF-Based Resin)
The PVDF-based resin included in the porous layer in accordance with an embodiment of the present invention is configured such that, assuming that the sum of the respective amounts of an α-form PVDF-based resin and a β-form PVDF-based resin contained in the PVDF-based resin is 100 mol %, the amount of the α-form PVDF-based resin contained in the PVDF-based resin is not less than 35.0 mol %, preferably not less than 37.0 mol %, more preferably not less than 40.0 mol %, even more preferably not less than 44.0 mol %. Further, the amount of the α-form PVDF-based resin is preferably not more than 90.0 mol %. The porous layer containing the α-form PVDF-based resin in an amount falling within the above range is suitably usable as a member of a nonaqueous electrolyte secondary battery in which a decrease in discharge capacity after charge-discharge cycles is reduced, in particular as a member of a nonaqueous electrolyte secondary battery laminated separator or as a member of an electrode of a nonaqueous electrolyte secondary battery.
The nonaqueous electrolyte secondary battery generates heat due to resistance inside the battery during charge and discharge, and calorific power increases as an electric current becomes higher, in other words, in a condition of higher rate. In the PVDF-based resin, a melting point of the α-form PVDF-based resin is higher than that of the β-form PVDF-based resin, and thus the α-form PVDF-based resin is less likely to cause plastic deformation by heat.
According to the porous layer in accordance with an embodiment of the present invention, a proportion of an α-form PVDF-based resin contained in the PVDF-based resin constituting the porous layer is controlled to a specific proportion or more, and this makes it possible to inhibit deformation of an internal structure of the porous layer, blockage of voids, and the like which are caused due to deformation of the PVDF-based resin that is caused by heat generated during charge and discharge operations. Consequently, it is possible to maintain a good high-rate characteristic after charge-discharge cycles.
The α-form PVDF-based resin is arranged such that the polymer of the PVDF-based resin contains a PVDF skeleton having molecular chains including a main-chain carbon atom bonded to a fluorine atom (or a hydrogen atom) adjacent to two carbon atoms one of which is bonded to a hydrogen atom (or a fluorine atom) having a trans position and the other one of which is bonded to a hydrogen atom (or a fluorine atom) having a gauche position (positioned at an angle of 60°), wherein two or more such conformations are chained consecutively as follows:
(TGTG Structure) [Math. 1]
and the molecular chains each have the following type:
TGTG [Math. 2]
wherein the respective dipole moments of C-F₂and C-H₂bonds each have a component perpendicular to the molecular chain and a component parallel to the molecular chain.
The α-form PVDF-based resin has characteristic peaks at around −95 ppm and at around −78 ppm in a ¹⁹F-NMR spectrum.
The β-form PVDF-based resin is arranged such that the polymer of the PVDF-based resin contains a PVDF skeleton having molecular chains including a main-chain carbon atom adjacent to two carbon atoms bonded to a fluorine atom and a hydrogen atom, respectively, each having a trans conformation (TT-type conformation), that is, the fluorine atom and the hydrogen atom bonded respectively to the two carbon atoms are positioned oppositely at an angle of 180° to the direction of the carbon-carbon bond.
The β-form PVDF-based resin may be arranged such that the polymer of the PVDF-based resin contains a PVDF skeleton that has a TT-type conformation in its entirety. The β-form PVDF-based resin may alternatively be arranged such that a portion of the PVDF skeleton has a TT-type conformation and that the β-form PVDF-based resin has a molecular chain of the TT-type conformation in at least four consecutive PVDF monomeric units. In either case, (i) the carbon-carbon bond, in which the TT-type conformation constitutes a TT-type main chain, has a planar zigzag structure, and (ii) the respective dipole moments of C-F₂and C—H₂bonds each have a component perpendicular to the molecular chain.
The β-form PVDF-based resin has characteristic peaks at around −95 ppm in a ¹⁹F-NMR spectrum.
(Method for Calculating Content Rates of α-Form PVDF-Based Resin and β-Form PVDF-Based Resin in PVDF-Based Resin)
The rate of content of the α-form PVDF-based resin and the rate of content of the β-form PVDF-based resin in the porous layer in accordance with an embodiment of the present invention relative to 100 mol % of the combined content of the α-form PVDF-based resin and the β-form PVDF-based resin may be calculated from a ¹⁹F-NMR spectrum obtained from the porous layer. The content rates are specifically calculated as follows, for example:
(1) A ¹⁹F-NMR spectrum is obtained from a porous layer containing a PVDF-based resin, under the following conditions.

Measurement Conditions

Measurement device: AVANCE400 manufactured by Bruker Biospin
Measurement method: single-pulse method
Observed nucleus: ¹⁹F
Spectral bandwidth: 100 kHz
Pulse width: 3.0 s (90° pulse)
Pulse repetition time: 5.0 s
Reference material: C₆F₆(external reference: −163.0 ppm)
Temperature: 22° C.
Sample rotation frequency: 25 kHz
(2) An integral value of a peak at around −78 ppm in the ¹⁹F-NMR spectrum obtained in (1) is calculated and is regarded as an α/2 amount.
(3) As with the case of (2), an integral value of a peak at around −95 ppm in the ¹⁹F-NMR spectrum obtained in (1) is calculated and is regarded as an {(α/2)+β} amount.
(4) Assuming that the sum of (i) the content of the α-form PVDF-based resin and (ii) the content of the β-form PVDF-based resin is 100 mol %, the rate of content of the α-form PVDF-based resin (hereinafter referred to also as “a rate”) is calculated from the integral values of (2) and (3) in accordance with the following Formula (2):
α rate (mol %)=[(integral value at around −78 ppm)×2/{(integral value at around −95 ppm)+(integral value at around −78 ppm)}]×100 (2)
(5) Assuming that the sum of (i) the content of the α-form PVDF-based resin and (ii) the content of the β-form PVDF-based resin is 100 mol %, the rate of content of the β-form PVDF-based resin (hereinafter referred to also as “β rate”) is calculated from the value of the α rate of (4) in accordance with the following Formula (3):
β rate (mol %)=100 (mol %)−α rate (mol %) (3)
(Method for Producing Porous Layer and Nonaqueous Electrolyte Secondary Battery Laminated Separator)
A method for producing each of the porous layer and the nonaqueous electrolyte secondary battery laminated separator in accordance with an embodiment of the present invention is not limited in particular, and any of various production methods may be employed.
According to the nonaqueous electrolyte secondary battery laminated separator, for example, a porous layer containing a PVDF-based resin and optionally a filler is formed through one of the processes (1) to (3) below on a surface of a porous film that serves as a base material. In the case of the process (2) or (3), a porous layer deposited is dried for removal of the solvent. In the case of production of a porous layer containing a filler, the coating solution in the processes (1) through (3) preferably contains a filler dispersed therein and a PVDF-based resin dissolved therein.
The coating solution for use in a method for producing a porous layer in accordance with an embodiment of the present invention can be prepared typically by (i) dissolving, in a solvent, a resin to be contained in the porous layer and, (ii) in a case where a filler is to be contained in the porous layer, dispersing the filler in the solvent.
(1) A process of (i) coating a surface of a porous film with a coating solution containing a PVDF-based resin to be contained in the porous layer and optionally a filler and (ii) drying the surface of the porous film to remove the solvent (dispersion medium) from the coating solution for formation of a porous layer.
(2) A process of (i) coating a surface of a porous film with the coating solution described in (1) and then (ii) immersing the porous film into a deposition solvent (which is a poor solvent for the PVDF-based resin) for deposition of a porous layer.
(3) A process of (i) coating a surface of a porous film with the coating solution described in (1) and then (ii) making the coating solution acidic with use of a low-boiling-point organic acid for deposition of a porous layer.
Examples of the solvent (dispersion medium) in the coating solution include N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, acetone, and water.
The deposition solvent is preferably isopropyl alcohol or t-butyl alcohol, for example.
For the process (3), the low-boiling-point organic acid can be, for example, paratoluene sulfonic acid or acetic acid.
The base material can be, other than a porous film, another film, a positive electrode plate, a negative electrode plate, or the like.
The coating solution may contain an additive(s) as appropriate such as a dispersing agent, a plasticizing agent, a surface active agent, and a pH adjusting agent as a component(s) other than the resin and the filler.
The coating solution can be applied to the base material by a conventionally publicly known method. Specific examples of such a method include a gravure coater method, a dip coater method, a bar coater method, and a die coater method.
(Method for Controlling Crystal Forms of PVDF-Based Resin)
The crystal form of the PVDF-based resin contained in the porous layer in accordance with an embodiment of the present invention can be controlled on the basis of (i) drying conditions such as the drying temperature, and the air velocity and air direction during drying in the above described method and (ii) the deposition temperature at which a porous layer containing a PVDF-based resin is deposited with use of a deposition solvent or a low-boiling-point organic acid.
Note that the drying conditions and the deposition temperature, which are adjusted so that the PVDF-based resin contains an α-form PVDF-based resin in an amount of not less than 35.0 mol % with respect to 100 mol % of the total amount of the α-form PVDF-based resin and a β-form PVDF-based resin contained, may be changed as appropriate by changing, for example, the method for producing a porous layer, the kind of solvent (dispersion medium) to be used, the kind of deposition solvent to be used, and/or the kind of low-boiling-point organic acid to be used.
In a case where the coating solution is simply dried as in the process (1), the drying conditions may be changed as appropriate by adjusting, for example, the amount of the solvent in the coating solution, the concentration of the PVDF-based resin in the coating solution, the amount of the filler (if contained), and/or the amount of the coating solution to be applied. In a case where a porous layer is to be formed through the above process (1), it is preferable that the drying temperature be 30° C. to 100° C., that the direction of hot air for drying be perpendicular to a nonaqueous electrolyte secondary battery separator or electrode plate to which the coating solution has been applied, and that the velocity of the hot air be 0.1 m/s to 40 m/s. Specifically, in a case where a coating solution to be applied contains N-methyl-2-pyrrolidone as the solvent for dissolving a PVDF-based resin, 1.0% by mass of a PVDF-based resin, and 9.0% by mass of alumina as an inorganic filler, the drying conditions are preferably adjusted so that the drying temperature is 40° C. to 100° C., that the direction of hot air for drying is perpendicular to a nonaqueous electrolyte secondary battery separator or an electrode plate to which the coating solution has been applied, and that the velocity of the hot air is 0.4 m/s to 40 m/s.
In a case where a porous layer is to be formed through the above process (2), it is preferable that the deposition temperature be −25° C. to 60° C. and that the drying temperature be 20° C. to 100° C. Specifically, in a case where a porous layer is to be formed through the above process (2) with use of N-methylpyrrolidone as the solvent for dissolving a PVDF-based resin and isopropyl alcohol as the deposition solvent, it is preferable that the deposition temperature be −10° C. to 40° C. and that the drying temperature be 30° C. to 80° C.
(Another Porous Layer)
The nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention can contain another porous layer in addition to (i) the porous film and (ii) the porous layer containing the PVDF-based resin. The another porous layer need only be provided between (i) the nonaqueous electrolyte secondary battery separator and (ii) at least one of the positive electrode plate and the negative electrode plate. The porous layer and the another porous layer may be provided in any order with respect to the nonaqueous electrolyte secondary battery separator. In a preferable configuration, the porous film, the another porous layer, and the porous layer containing the PVDF-based resin are disposed in this order. In other words, the another porous layer is provided between the porous film and the porous layer containing the PVDF-based resin. In another preferable configuration, the another porous layer and the porous layer containing the PVDF-based resin are provided in this order on both surfaces of the porous film.
Examples of a resin which can be contained in the another porous layer in accordance with an embodiment of the present invention encompass: polyolefins; (meth)acrylate-based resins; fluorine-containing resins (excluding polyvinylidene fluoride-based resins); polyamide-based resins; polyimide-based resins; polyester-based resins; rubbers; resins with a melting point or glass transition temperature of not lower than 180° C.; water-soluble polymers; polycarbonate, polyacetal, and polyether ether ketone.
Among the above resins, polyolefins, (meth)acrylate-based resins, polyamide-based resins, polyester-based resins, and water-soluble polymers are preferable.
Preferable examples of the polyolefin encompass polyethylene, polypropylene, polybutene, and an ethylene-propylene copolymer.
Examples of the fluorine-containing resins encompass polytetrafluoroethylene, a vinylidene fluoride-hexafluoropropylene copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer, a vinylidene fluoride-trifluoroethylene copolymer, a vinylidene fluoride-trichloroethylene copolymer, a vinylidene fluoride-vinyl fluoride copolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and an ethylene-tetrafluoroethylene copolymer. Particular examples of the fluorine-containing resins encompass fluorine-containing rubber having a glass transition temperature of not higher than 23° C.
Preferable examples of the polyamide-based resin encompass aramid resins such as aromatic polyamide and wholly aromatic polyamide.
Specific examples of the aramid resin encompass poly(paraphenylene terephthalamide), poly(methaphenylene isophthalamide), poly(parabenzamide), poly(metabenzamide), poly(4,4′-benzanilide terephthalamide), poly(paraphenylene-4,4′-biphenylene dicarboxylic acid amide), poly(methaphenylene-4,4′-biphenylene dicarboxylic acid amide), poly(paraphenylene-2,6-naphthalene dicarboxylic acid amide), poly(methaphenylene-2,6-naphthalene dicarboxylic acid amide), poly(2-chloroparaphenylene terephthalamide), a paraphenylene terephthalamide/2,6-dichloroparaphenylene terephthalamide copolymer, and a methaphenylene terephthalamide/2,6-dichloroparaphenylene terephthalamide copolymer. Among these aramid resins, poly(paraphenylene terephthalamide) is more preferable.
Preferable examples of the polyester-based resin encompass (i) aromatic polyesters such as polyarylate and (ii) liquid crystal polyesters.
Examples of the rubbers encompass a styrene-butadiene copolymer and a hydride thereof, a methacrylic acid ester copolymer, an acrylonitrile-acrylic acid ester copolymer, a styrene-acrylic acid ester copolymer, an ethylene propylene rubber, and polyvinyl acetate.
Examples of the resin with a melting point or a glass transition temperature of not lower than 180° C. encompass polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamide imide, and polyether amide.
Examples of the water-soluble polymer encompass polyvinyl alcohol, polyethylene glycol, cellulose ether, sodium alginate, polyacrylic acid, polyacrylamide, and polymethacrylic acid.
Only one kind of these resins to be contained in the another porous layer can be used, or two or more kinds of these resins can be used in combination.
The other characteristics (e.g., thickness) of the another porous layer are similar to the characteristics described in Section [4. Porous layer] above, except that the porous layer contains the PVDF-based resin.
[5. Nonaqueous Electrolyte]
A nonaqueous electrolyte that can be contained in the nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention is not limited to any particular one, provided that the nonaqueous electrolyte is one that is generally used for a nonaqueous electrolyte secondary battery. The nonaqueous electrolyte can be a nonaqueous electrolyte containing, for example, an organic solvent and a lithium salt dissolved therein. Examples of the lithium salt encompass LiClO₄, LiPF₆, LiAsF₆, LiSbF₆, LiBF₄, LiCF₃SO₃, LiN(CF₃SO₂)₂, LiC(CF₃SO₂)₃, Li₂B₁₀Cl₁₀, lower aliphatic carboxylic acid lithium salt, and LiAlCl₄. It is possible to use only one kind of the above lithium salts or two or more kinds of the above lithium salts in combination.
Examples of the organic solvent to be contained in the nonaqueous electrolyte encompass carbonates, ethers, esters, nitriles, amides, carbamates, and sulfur-containing compounds, and fluorine-containing organic solvents each obtained by introducing a fluorine group into any of these organic solvents. It is possible to use only one kind of the above organic solvents or two or more kinds of the above organic solvents in combination.
[6. Method for Producing Nonaqueous Electrolyte Secondary Battery]
The nonaqueous electrolyte secondary battery in accordance with an embodiment of the present invention can be produced by, for example, (i) forming a nonaqueous electrolyte secondary battery member in which the positive electrode plate, the nonaqueous electrolyte secondary battery laminated separator, and the negative electrode plate are arranged in this order, (ii) then inserting the nonaqueous electrolyte secondary battery member into a container for use as a housing of the nonaqueous electrolyte secondary battery, (iii) then filling the container with a nonaqueous electrolyte, and (iv) then hermetically sealing the container under reduced pressure.
The present invention is not limited to the embodiments, but can be altered by a skilled person in the art within the scope of the claims. The present invention also encompasses, in its technical scope, any embodiment derived by combining technical means disclosed in differing embodiments.

EXAMPLES

[Method for Measuring Various Physical Properties]
Various physical properties of nonaqueous electrolyte secondary batteries in accordance with the Examples and Comparative Examples were measured by the following methods:
(1) Film Thicknesses (Porous Film, Positive Electrode Active Material Layer, and Negative Electrode Active Material Layer)
The respective thicknesses of a porous film, a positive electrode active material layer, and a negative electrode active material layer were measured with use of a high-accuracy digital length measuring machine (VL-50) available from Mitutoyo Corporation. The thickness of a positive electrode active material layer was calculated by subtracting the thickness of an aluminum foil as a current collector from the thickness of the positive electrode plate. The thickness of a negative electrode active material layer was calculated by subtracting the thickness of a copper foil as a current collector from the thickness of the negative electrode plate.
(2) Temperature Rise Ending Period at Microwave Irradiation (Porous Film)
An 8 cm×8 cm test piece was cut out from a porous film, and a weight W (g) of the test piece was measured. Then, a weight per unit area of the test piece was calculated in accordance with the following formula: Weight per unit area (g/m²)=W/(0.08×0.08).
Next, the test piece was impregnated with N-methylpyrrolidone (NMP) to which 3% by weight of water had been added. Then, the test piece was placed on a Teflon (registered trademark) sheet (12 cm×10 cm). The test piece was folded in half in such a manner as to sandwich an optical fiber thermometer (manufactured by ASTEC Co., Ltd., Neoptix Reflex thermometer) coated with polytetrafluoroethylene (PTFE).
Next, the test piece, which had been impregnated with NMP containing water and had been so folded as to sandwich the thermometer, was fixed in a microwave irradiation device (manufactured by Micro Denshi Co., Ltd., 9-kW microwave oven; frequency: 2455 MHz) equipped with a turntable. The test piece was then irradiated with a microwave at 1800 W for 2 minutes. Note that a surface temperature of the film immediately before microwave irradiation was adjusted to 29±1° C.
An air temperature inside the device at the microwave irradiation was 27° C. to 30° C.
The optical fiber thermometer was used to measure, every 0.2 seconds, changes in the temperature of the test piece after the start of the microwave irradiation. In the temperature measurements, the temperature at which no temperature rise was measured for not less than 1 second was used as a temperature rise ending temperature, and the time period that elapsed before the temperature rise ending temperature was reached after the start of the microwave irradiation was used as a temperature rise ending period. The temperature rise ending period thus obtained was divided by the above weight per unit area for calculation of a temperature rise ending period per weight per unit area. The “temperature rise ending period per weight per unit area” is synonymous with a “temperature rise ending period with respect to the amount of resin per unit area”.
(3) Rate of Content of α-Form PVDF-Based Resin (Porous Layer)
A piece with a size of approximately 2 cm×5 cm was cut out from each of the laminated porous films produced in the Examples and Comparative Examples below. Then, the rate of content (a rate) of the α-form PVDF-based resin in the PVDF-based resin contained in the cutout was measured through the above steps (1) to (4) described in the (Method for calculating content rates of α-form PVDF-based resin and β-form PVDF-based resin in PVDF-based resin)” section.
(4) Respective Average Particle Diameters of Positive Electrode Active Material and Negative Electrode Active Material
The volume-based particle size distribution and average particle diameter (D50) were measured with use of a laser diffraction particle size analyzer (product name: SALD2200, manufactured by Shimadzu Corporation).
(5) Porosity (Electrode Active Material Layer)
The porosity c of the positive electrode active material layer or negative electrode active material layer was calculated in accordance with the formula shown in the “(Positive electrode plate)” section.
(6) Sum of Interface Barrier Energies
The sum of the interface barrier energies was calculated through the steps (1) to (5) described in the “(Sum of interface barrier energies)” section.
(7) Discharge Capacity at 5 C after 100 Charge-Discharge Cycles
Discharge capacity at 5 C after 100 charge-discharge cycles was measured through the steps (1) through (3) described in Section [1. Nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention].

Example 1

[Production of Nonaqueous Electrolyte Secondary Battery Laminated Separator]
Ultra-high molecular weight polyethylene powder (GUR4032, available from Ticona Corporation; weight-average molecular weight: 4,970,000) and polyethylene wax (FNP-0115, available from Nippon Seiro Co., Ltd.) having a weight-average molecular weight of 1000 were mixed at a ratio of 70% by weight:30% by weight. Then, to 100 parts by weight of a mixture of the ultra-high molecular weight polyethylene and the polyethylene wax, the following were added: 0.4 parts by weight of antioxidant (Irg1010, available from Ciba Specialty Chemicals Inc.), 0.1 parts by weight of antioxidant (P168, available from Ciba Specialty Chemicals Inc.), and 1.3 parts by weight of sodium stearate. Then, calcium carbonate (available from Maruo Calcium Co., Ltd.) having an average particle diameter of 0.1 μm was further added so as to account for 36% by volume of the total volume of the resultant mixture. Then, the resultant mixture while remaining a powder was mixed with the use of a Henschel mixer, so that a mixture 1 was obtained.
Thereafter, the mixture 1 was melted and kneaded with the use of a twin screw kneading extruder, so that a polyolefin resin composition 1 was obtained. Then, the polyolefin resin composition 1 was rolled with the use of a roller at a circumferential velocity of 3.0 m/min, so that a rolled sheet 1 was obtained. Then, the rolled sheet 1 was immersed in an aqueous hydrochloric acid solution (containing 4 mol/L of hydrochloric acid and 0.5% by weight of a nonionic surfactant) for removal of the calcium carbonate from the rolled sheet 1, and was then stretched 6.2-fold at 105° C. (ratio of the stretch temperature to the stretch magnification=16.9). This film was then subjected to heat fixation at 120° C. This produced a porous film 1. The weight per unit area of the porous film 1 produced was 6.9 g/m².
An N-methyl-2-pyrrolidone solution (manufactured by Kureha Corporation; product name: L#9305, weight-average molecular weight: 1,000,000) containing a PVDF-based resin was prepared as a coating solution. The coating solution was applied to the porous film 1. The PVDF-based resin used in the N-methyl-2-pyrrolidone solution was polyvinylidene fluoride-hexafluoropropylene copolymer. The application of the coating solution was carried out by a doctor blade method, and so that the applied coating solution was adjusted to weigh 6.0 g per square meter of the PVDF-based resin in the coating solution.
The porous film, to which the coating solution had been applied, was immersed into 2-propanol while the coating film was wet with the solvent, and was then left to stand still at −10° C. for 5 minutes. This produced a laminated porous film 1. The laminated porous film 1 produced was further immersed into other 2-propanol while the laminated porous film 1 was wet with the above immersion solvent, and was then left to stand still at 25° C. for 5 minutes. This produced a laminated porous film 1a. The laminated porous film 1a produced was dried at 30° C. for 5 minutes. This produced a nonaqueous electrolyte secondary battery laminated separator 1 including a porous layer. Table 1 shows results of evaluation of the porous film 1 and the nonaqueous electrolyte secondary battery laminated separator 1 produced.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
(Positive Electrode Plate)
A positive electrode plate was obtained in which a positive electrode mix (LiNi_0.5Mn_0.3Co_0.2O₂/electrically conductive agent/PVDF (weight ratio of 92:5:3)) was disposed on one surface of a positive electrode current collector (aluminum foil). LiNi_0.5Mn_0.3Co_0.2O₂had a volume-based average particle diameter (D50) of 5 μm. In the positive electrode plate thus obtained, a positive electrode active material layer had a porosity of 40%.
The positive electrode plate was partially cut off as a positive electrode plate 1 that was constituted by (i) a portion which had a size of 45 mm×30 mm and on which a positive electrode active material layer was disposed and (ii) a portion which surrounded an outer periphery of the portion of (i) and had a width of 13 mm and on which the positive electrode active material layer was not disposed.
(Negative Electrode Plate)
A negative electrode plate was obtained in which a negative electrode mix (natural graphite/styrene-1,3-butadiene copolymer/sodium carboxymethylcellulose (weight ratio of 98:1:1) was disposed on one surface of a negative electrode current collector (copper foil). The natural graphite had a volume-based average particle diameter (D50) of 15 μm. In the obtained negative electrode plate, the negative electrode active material layer had a porosity of 31%.
The negative electrode plate was partially cut off as a negative electrode plate 1 that was constituted by (i) a portion which had a size of 50 mm×35 mm and on which a negative electrode active material layer was disposed and (ii) a portion which surrounded an outer periphery of the portion of (i) and had a width of 13 mm and on which the negative electrode active material layer was not disposed.
As can be seen from the above description, with regard to the positive electrode plate 1 and the negative electrode plate 1, (the particle diameter of the negative electrode active material)/(the particle diameter of the positive electrode active material) gave 3.0. Table 1 shows the results of evaluation of the sum of the respective interface barrier energies measured of the positive electrode plate 1 and the negative electrode plate 1.
(Assembly of Nonaqueous Electrolyte Secondary Battery)
The following method was used for preparing a nonaqueous electrolyte secondary battery by using the positive electrode plate 1, the negative electrode plate 1, and the nonaqueous electrolyte secondary battery laminated separator 1.
In a laminate pouch, the positive electrode plate 1, the nonaqueous electrolyte secondary battery laminated separator 1 with the porous layer facing the positive electrode, and the negative electrode plate 1 were disposed (arranged) on top of one another so as to obtain a nonaqueous electrolyte secondary battery member 1. During this operation, the positive electrode plate 1 and the negative electrode plate 1 were arranged so that the positive electrode active material layer of the positive electrode plate 1 had a main surface that was entirely covered by the main surface of the negative electrode active material layer of the negative electrode plate 1.
Subsequently, the nonaqueous electrolyte secondary battery member 1 was put into a bag prepared in advance from a laminate of an aluminum layer and a heat seal layer. Further, 0.23 mL of nonaqueous electrolyte was put into the bag. The above nonaqueous electrolyte was prepared by dissolving LiPF₆in a mixed solvent of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate at a ratio of 3:5:2 (volume ratio) so that the LiPF₆would be contained at 1 mol/L. The bag was then heat-sealed while the pressure inside the bag was reduced. This produced a nonaqueous electrolyte secondary battery 1.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 1 obtained by the above described method was measured. Table 1 shows the measurement results.

Example 2

[Production of Nonaqueous Electrolyte Secondary Battery Laminated Separator]
The substances (i) below were mixed in powder form with use of a Henschel mixer.
Further, the substances (ii) and (iii) below were added and were then mixed in powder form with use of the Henschel mixer. Thereafter, the resulting mixture was melted and kneaded in a twin screw kneading extruder. This produced a polyolefin resin composition.
(i) 70% by weight of ultra-high molecular weight polyethylene powder (GUR4032, manufactured by Ticona Corporation) having a weight-average molecular weight of 4,970,000, and 30% by weight of polyethylene wax (FNP-0115, manufactured by Nippon Seiro Co., Ltd.) having a weight-average molecular weight of 1,000;
(ii) 0.4 parts by weight of an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals Corporation), 0.1 parts by weight of an antioxidant (P168, manufactured by Ciba Specialty Chemicals Corporation), and 1.3 parts by weight of sodium stearate (note that a total weight of (i) is defined as 100 parts by weight); and
(iii) 36% by volume of calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average particle diameter of 0.1 μm (note that a total volume of (i) through (iii) is defined as 100% by volume).
Then, the polyolefin resin composition was rolled into a sheet with use of a pair of rollers each having a surface temperature of 150° C. This sheet was immersed in an aqueous hydrochloric acid solution (containing 4 mol/L of hydrochloric acid and 0.5% by weight of nonionic surfactant) for removal of the calcium carbonate. The sheet was then stretched 6.2-fold at 100° C. to 105° C. at a straining rate of 750% per minute. This prepared a film having a thickness of 16.3 μm. This film was then subjected to heat fixation at 115° C. This produced a porous film 2.
A coating solution was applied to the porous film 2 in a manner similar to that of Example 1. The porous film, to which the coating solution had been applied, was immersed into 2-propanol while the coating film was wet with the solvent, and was then left to stand still at 25° C. for 5 minutes. This produced a laminated porous film 2. The laminated porous film 2 produced was further immersed into other 2-propanol while the laminated porous film 1 was wet with the above immersion solvent, and was then left to stand still at 25° C. for 5 minutes. This produced a laminated porous film 2a. The laminated porous film 2a produced was dried at 65° C. for 5 minutes. This produced a nonaqueous electrolyte secondary battery laminated separator 2 including a porous layer. Table 1 shows results of evaluation of the porous film 2 and the nonaqueous electrolyte secondary battery laminated separator 2 produced.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
A nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1, except that the nonaqueous electrolyte secondary battery laminated separator 2 was used instead of the nonaqueous electrolyte secondary battery laminated separator 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 2”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 2 obtained by the above described method was measured. Table 1 shows the measurement results.

Example 3

[Production of Nonaqueous Electrolyte Secondary Battery Laminated Separator]
The substances (i) below were mixed in powder form with use of a Henschel mixer.
Further, the substances (ii) and (iii) below were added and were then mixed in powder form with use of the Henschel mixer. Thereafter, the resulting mixture was melted and kneaded in a twin screw kneading extruder. This produced a polyolefin resin composition.
(i) 71% by weight of ultra-high molecular weight polyethylene powder (GUR4032, manufactured by Ticona Corporation) having a weight-average molecular weight of 4,970,000, and 29% by weight of polyethylene wax (FNP-0115, manufactured by Nippon Seiro Co., Ltd.) having a weight-average molecular weight of 1,000;
(ii) 0.4 parts by weight of an antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals Corporation), 0.1 parts by weight of an antioxidant (P168, manufactured by Ciba Specialty Chemicals Corporation), and 1.3 parts by weight of sodium stearate (note that a total weight of (i) is defined as 100 parts by weight); and
(iii) 37% by volume of calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average particle diameter of 0.1 μm (note that a total volume of (i) through (iii) is defined as 100% by volume).
Then, the polyolefin resin composition was rolled into a sheet with use of a pair of rollers each having a surface temperature of 150° C. This sheet was immersed in an aqueous hydrochloric acid solution (containing 4 mol/L of hydrochloric acid and 0.5% by weight of nonionic surfactant) for removal of the calcium carbonate. The sheet was then stretched 7.0-fold at 100° C. to 105° C. at a straining rate of 2100% per minute. This prepared a film having a thickness of 11.7 μm. This film was then subjected to heat fixation treatment at 123° C. This produced a porous film 3.
A coating solution was applied to the porous film 3 in a manner similar to that of Example 1. The porous film, to which the coating solution had been applied, was immersed into 2-propanol while the coating film was wet with the solvent, and was then left to stand still at −5° C. for 5 minutes. This produced a laminated porous film 3. The laminated porous film 3 produced was further immersed into other 2-propanol while the laminated porous film 3 was wet with the above immersion solvent, and was then left to stand still at 25° C. for 5 minutes. This produced a laminated porous film 3a. The laminated porous film 3a produced was dried at 30° C. for 5 minutes. This produced a nonaqueous electrolyte secondary battery laminated separator 3 including a porous layer. Table 1 shows results of evaluation of the porous film 3 and the nonaqueous electrolyte secondary battery laminated separator 3 produced.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
A nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1, except that the nonaqueous electrolyte secondary battery laminated separator 3 was used instead of the nonaqueous electrolyte secondary battery laminated separator 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 3”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 3 obtained by the above described method was measured. Table 1 shows the measurement results.

Example 4

(Positive Electrode Plate)
A positive electrode plate was obtained in which a positive electrode mix (LiCoO₂/electrically conductive agent/PVDF (weight ratio of 100:5:3)) was disposed on one surface of a positive electrode current collector (aluminum foil). LiCoO₂had a volume-based average particle diameter (D50) of 13 μm. In the positive electrode plate thus obtained, a positive electrode active material layer had a porosity of 31%.
The positive electrode plate was partially cut off as a positive electrode plate 2 that was constituted by (i) a portion which had a size of 45 mm×30 mm and on which a positive electrode active material layer was disposed and (ii) a portion which surrounded an outer periphery of the portion of (i) and had a width of 13 mm and on which the positive electrode active material layer was not disposed.
As can be seen from the above description as well as the description in Example 1, with regard to the positive electrode plate 2 and the negative electrode plate 1, (the particle diameter of the negative electrode active material)/(the particle diameter of the positive electrode active material) gave 1.1. Table 1 shows the results of evaluation of the sum of the respective interface barrier energies measured of the positive electrode plate 2 and the negative electrode plate 1.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
The positive electrode plate 2 was used as a positive electrode plate, the negative electrode plate 1 was used as a negative electrode plate, and the nonaqueous electrolyte secondary battery laminated separator 3 was used as a nonaqueous electrolyte secondary battery laminated separator. Except for those, a nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 4”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 4 obtained by the above described method was measured. Table 1 shows the measurement results.

Example 5

[Preparation of Porous Layer and Nonaqueous Electrolyte Secondary Battery Laminated Separator]
In N-methyl-2-pyrrolidone, a PVDF-based resin (product name: “Kynar (registered trademark) LBG”, available from Arkema Inc.; weight-average molecular weight of 590,000) was stirred and dissolved at 65° C. for 30 minutes. Note that the solid content in the solution after the dissolution was controlled to 10% by mass. The solution thus obtained was used as a binder solution. As a filler, alumina fine particles (manufactured by Sumitomo Chemical Co., Ltd.; product name “AKP3000”; containing 5 ppm of silicon) was used. The alumina fine particles, the binder solution, and a solvent (N-methyl-2-pyrrolidone) were mixed together in the following proportion. That is, the alumina fine particles, the binder solution, and the solvent were mixed together so that (i) a resultant mixed solution contained 10 parts by weight of the PVDF-based resin with respect to 90 parts by weight of the alumina fine particles and (ii) a solid content concentration (alumina fine particles+PVDF-based resin) of the mixed solution was 10% by weight. A dispersion solution was thus obtained. The dispersion solution thus obtained was used as a coating solution.
The coating solution was applied by a doctor blade method to the porous film 3 prepared in Example 3, so that the applied coating solution weighed 6.0 g per square meter of the PVDF-based resin in the coating solution. This produced a laminated porous film 3. The laminated porous film 3 was dried at 65° C. for 5 minutes. This produced a nonaqueous electrolyte secondary battery laminated separator 3 including a porous layer. The drying operation involved hot air blown in an air direction perpendicular to the base material at an air velocity of 0.5 m/s. Table 1 shows a result of evaluation of the nonaqueous electrolyte secondary battery laminated separator 4 produced.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
A nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1, except that the nonaqueous electrolyte secondary battery laminated separator 4 was used instead of the nonaqueous electrolyte secondary battery laminated separator 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 5”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 5 obtained by the above described method was measured. Table 1 shows the measurement results.

Comparative Example 1

[Preparation of Nonaqueous Electrolyte Secondary Battery Laminated Separator]
A porous film to which a coating solution had been applied as in Example 3 was immersed into 2-propanol while the coating film was wet with the solvent, and was then left to stand still at −78° C. for 5 minutes. This produced a laminated porous film 5. The laminated porous film 5 produced was further immersed into other 2-propanol while the laminated porous film 5 was wet with the above immersion solvent, and was then left to stand still at 25° C. for 5 minutes. This produced a laminated porous film 5a. The laminated porous film 5a produced was dried at 30° C. for 5 minutes. This produced a nonaqueous electrolyte secondary battery laminated separator 5 including a porous layer. Table 1 shows a result of evaluation of the nonaqueous electrolyte secondary battery laminated separator 5 produced.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
A nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1, except that the nonaqueous electrolyte secondary battery laminated separator 5 was used instead of the nonaqueous electrolyte secondary battery laminated separator 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 6”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 6 obtained by the above described method was measured. Table 1 shows the measurement results.

Comparative Example 2

(Negative Electrode Plate)
A negative electrode plate was obtained in which a negative electrode mix (artificial spherocrystal graphite/electrically conductive agent/PVDF (weight ratio of 85:15:7.5)) was disposed on one surface of a negative electrode current collector (copper foil). The artificial spherocrystal graphite had a volume-based average particle diameter (D50) of 34 μm. In the obtained negative electrode plate, the negative electrode active material layer had a porosity of 34%.
The negative electrode plate was partially cut off as a negative electrode plate 2 that was constituted by (i) a portion which had a size of 50 mm×35 mm and on which a negative electrode active material layer was disposed and (ii) a portion which surrounded an outer periphery of the portion of (i) and had a width of 13 mm and on which the negative electrode active material layer was not disposed.
As can be seen from the above description as well as the description in Example 1, with regard to the positive electrode plate 1 and the negative electrode plate 2, (the particle diameter of the negative electrode active material)/(the particle diameter of the positive electrode active material) gave 6.8. Table 1 shows the results of evaluation of the sum of the respective interface barrier energies measured of the positive electrode plate 1 and the negative electrode plate 2.
[Preparation of Nonaqueous Electrolyte Secondary Battery]
The positive electrode plate 1 was used as a positive electrode plate, the negative electrode plate 2 was used as a negative electrode plate, and the nonaqueous electrolyte secondary battery laminated separator 3 was used as a nonaqueous electrolyte secondary battery laminated separator. Except for those, a nonaqueous electrolyte secondary battery was prepared in a manner similar to that of Example 1. The nonaqueous electrolyte secondary battery thus prepared is hereinafter referred to as “nonaqueous electrolyte secondary battery 7”.
After that, discharge capacity at 5 C after 100 charge-discharge cycles of the nonaqueous electrolyte secondary battery 7 obtained by the above described method was measured. Table 1 shows the measurement results.

	TABLE 1

			Nonaqueous
	Nonaqueous electrolyte		electrolyte
	secondary battery laminated		Secondary
	separator		battery

Porous film		Electrode	Discharge
Temperature	Porous layer	plates	capacity at 5 C
rise ending	Content	Sum of	after 100
period/	of α-	interface	charge-
weight	form PVDF-	barrier	discharge
per unit area	based resin	energies	cycles
(sec · m²/g)	(mol %)	(J/mol)	(mAh/g)

Example 1	2.9	35.3	9069	135
Example 2	5.62	80.8	9069	134
Example 3	5.26	44.4	9069	120
Example 4	5.26	44.4	12612	121
Example 5	5.26	64.3	9069	130
Comparative	5.26	34.6	9069	107
Example 1
Comparative	5.26	44.4	4883	103
Example 2

(Results)
In all the Examples 1 through 5, (i) the α rate of the polyvinylidene fluoride-based resin contained in the porous layer was not less than 35.0 mol % and (ii) the sum of the interface barrier energies was not less than 5000 J/mol. Therefore, the discharge capacity at 5 C after 100 charge-discharge cycles was a preferable value, that is, not less than 120 mAh/g.
On the other hand, Comparative Examples failed to satisfy any of the conditions. Specifically, (i) in Comparative Example 1, the α rate of the polyvinylidene fluoride-based resin contained in the porous layer was less than 35.0 mol %, and (ii) in Comparative Example 2, the sum of the interface barrier energies was less than 5000 J/mol. Consequently, in all the Comparative Examples, the discharge capacity at 5 C after 100 charge-discharge cycles was less than 120 mAh/g.

Referential Example: Control of Interface Barrier Energies

A positive electrode plate and a negative electrode plate were prepared for which adjustment had been made to the particle diameter ratio between a positive electrode active material and a negative electrode active material.
The sum of the respective interface barrier energies was measured. Specifically, a positive electrode plate and a negative electrode plate were prepared with respective active materials having particle diameters changed from those in Example 1 as below while the compositions of the respective electrode plates were identical to those in Example 1. Table 2 shows the results of measurement of the sum of the respective interface barrier energies of the positive electrode plate and the negative electrode plate.
Further, a nonaqueous electrolyte secondary battery was prepared as in Example 1 except that the above positive electrode plate and negative electrode plate were used. The discharge capacity of the nonaqueous electrolyte secondary battery at 5 C after 100 charge-discharge cycles was measured. Table 2 shows the results.

TABLE 2

	Average
Average	particle			Discharge
particle	diameter			capacity at
diameter	of			5 C after
of positive	negative		Sum of	100
electrode	electrode		interface	charge-
active	active	Particle	barrier	discharge
material	material	diameter	energies	cycles
(μm)	(μm)	ratio	(J/mol)	(mAh/g)

Example 1	5	15	3	9069	135
Referential	0.8	20.3	24.7	4228	108
Example

(Results)
The positive electrode plate and the negative electrode plate in Example 1 were identical in composition to the positive electrode plate and the negative electrode plate in the Referential Example. The particle diameter ratio between the positive electrode active material and the negative electrode active material (a value given by (the particle diameter of the negative electrode active material/the particle diameter of the positive electrode active material)) was 3 in Example 1, but was 24.7 in the Referential Example. The sum of the respective interface barrier energies was 9069 J/mol in Example 1, but was only 4228 J/mol in the Referential Example.
These experimental results show that the sum of the interface barrier energies can be effectively controlled by, for example, adjusting the particle diameter ratio between the positive electrode active material and the negative electrode active material. It is needless to say that the sum of the interface barrier energies may be controlled by another method.
The discharge capacity at 5 C after 100 charge-discharge cycles was 135 mAh/g in Example 1, but was only 108 mAh/g in the Referential Example. These experimental results more clearly show that controlling the sum of the interface barrier energies to a predetermined value is one factor in maintaining a good high-rate discharge capacity after charge-discharge cycles.

INDUSTRIAL APPLICABILITY

A nonaqueous electrolyte secondary battery in accordance with an aspect of the present invention maintains a good high-rate discharge capacity after charge-discharge cycles. Therefore, the present invention is suitably applicable to (i) batteries for use in a personal computer, a mobile telephone, a portable information terminal, and the like and (ii) on-vehicle batteries.

Claims

1. A nonaqueous electrolyte secondary battery comprising:

a nonaqueous electrolyte secondary battery separator including a polyolefin porous film;

a porous layer containing a polyvinylidene fluoride-based resin;

a positive electrode plate; and

a negative electrode plate,

in a case where the positive electrode plate and the negative electrode plate have each been processed into a disk having a diameter of 15.5 mm and immersed in a solution of ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate which solution contains LiPF₆at a concentration of 1 M, a sum of respective interface barrier energies measured of a positive electrode active material and a negative electrode active material being not less than 5000 J/mol,

the polyolefin porous film having a temperature rise ending period of 2.9 seconds·m²/g to 5.7 seconds·m²/g with respect to an amount of resin per unit area in a case where the polyolefin porous film has been impregnated with N-methylpyrrolidone containing 3% by weight of water and has then been irradiated with a microwave having a frequency of 2455 MHz and an output of 1800 W,

the porous layer being provided between the nonaqueous electrolyte secondary battery separator and at least one of the positive electrode plate and the negative electrode plate,

the polyvinylidene fluoride-based resin contained in the porous layer containing an α-form polyvinylidene fluoride-based resin in an amount of not less than 35.0 mol % with respect to 100 mol % of a combined amount of the α-form polyvinylidene fluoride-based resin and a β-form polyvinylidene fluoride-based resin contained in the polyvinylidene fluoride-based resin,

a content of the α-form polyvinylidene fluoride-based resin being calculated by (i) waveform separation of (α/2) observed at around −78 ppm in a ¹⁹F-NMR spectrum obtained from the porous layer and (ii) waveform separation of {(α/2)+β} observed at around −95 ppm in the ¹⁹F-NMR spectrum obtained from the porous layer.

2. The nonaqueous electrolyte secondary battery as set forth in claim 1, wherein the positive electrode plate contains a transition metal oxide.

3. The nonaqueous electrolyte secondary battery as set forth in claim 1, wherein the negative electrode plate contains graphite.

4. The nonaqueous electrolyte secondary battery as set forth in claim 1, further comprising:

another porous layer which is provided between (i) the nonaqueous electrolyte secondary battery separator and (ii) at least one of the positive electrode plate and the negative electrode plate.

5. The nonaqueous electrolyte secondary battery as set forth in claim 4, wherein the another porous layer contains at least one resin selected from the group consisting of a polyolefin, a (meth)acrylate-based resin, a fluorine-containing resin (excluding a polyvinylidene fluoride-based resin), a polyamide-based resin, a polyester-based resin, and a water-soluble polymer.

6. The nonaqueous electrolyte secondary battery as set forth in claim 5, wherein the polyamide-based resin is aramid resin.